ZSM-5分子筛固定床催化合成聚甲氧基二甲醚

doi:10.16085/j.issn.1000-6613.2021-0907

摘要/Abstract

摘要：

通过X射线衍射（XRD）、扫描电子显微镜（SEM）、氨气程序升温脱附（NH₃-TPD）和吡啶吸附-红外光谱（Py-IR）等对不同硅铝比（SiO₂/Al₂O₃）的ZSM-5分子筛粉末催化剂进行表征。在间歇反应器中，本文对比了不同硅铝比ZSM-5分子筛粉末催化三聚甲醛和甲缩醛合成聚甲氧基二甲醚（PODE）的催化活性，结果表明硅铝比为400的ZSM-5分子筛粉末具有最高的PODE_2~8的收率和选择性。然后，采用挤条成型法，在ZSM-5分子筛粉末（SiO₂/Al₂O₃=400）中加入硅溶胶黏结剂和甲基纤维素黏结剂，制备得到ZSM-5成型催化剂，硅溶胶添加量和甲基纤维素分子量影响成型催化剂强度。采用ZSM-5成型催化剂，以固定床为反应器，反应温度和反应空速在所考察的范围内对三聚甲醛（TOX）的转化率和PODE的选择性影响较小。在85℃、压力1MPa、空速为5h^-1的条件下进行了240h催化性能考察，成型催化剂催化性能稳定，三聚甲醛的转化率高于90%，PODE_2~8的选择性达到95%以上。

关键词: 聚甲氧基二甲醚, 合成, 分子筛, 催化剂, 固定床

Abstract:

The ZSM-5 zeolite powders with different silica/alumina ratios(SiO₂/Al₂O₃) were characterized by XRD, SEM, NH₃?TPD and Py-IR. The catalytic performance of the ZSM-5 zeolites was compared in the synthesis of polyoxymethylene dimethyl ethers (PODE) from trioxane and methylal in a batch reactor. The ZSM-5 catalyst with SiO₂/Al₂O₃molar ratio of 400 showed the highest yield and selectivity of PODE_2-8. Then, the extruded ZSM-5 catalyst were prepared from the ZSM-5 powder (SiO₂/Al₂O₃=400) by adding silica sol and methyl cellulose as binder. The mechanical strength of the extruded ZSM-5 catalyst was influenced by the adding amount of silica sol and the molecular weight of methyl cellulose. The extruded ZSM-5 catalyst were used to synthesize PODE in a fixed-bed reactor. Temperature and space velocity had little effect on the conversion of trioxane and the selectivity of PODE under the conditions examined. When the reaction temperature was 85℃ and space velocity was 5h^-1 in the fixed-bed reactor, the extruded ZSM-5 catalyst showed excellent stability in a 240h test, and the conversion of trioxane was higher than 90%, and the selectivity of PODE_2~8 was above 95%.

Key words: polyoxymethylene dimethyl ethers, synthesis, molecular sieves, catalysts, fixed-bed

中图分类号:

O643

雷骞, 梁琳琳, 吕高孟, 陈洪林. ZSM-5分子筛固定床催化合成聚甲氧基二甲醚[J]. 化工进展, 2022, 41(4): 1908-1915.

LEI Qian, LIANG Linlin, LYU Gaomeng, CHEN Honglin. Synthesis of polyoxymethylene dimethyl ethers with shaped ZSM-5 catalysts in a fixed-bed reactor[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 1908-1915.

图/表 12

图1 不同硅铝比ZSM-5的XRD谱图和NH3-TPD图

表1 不同硅铝比ZSM-5的XRF和NH3-TPD表征结果

样品	SiO₂ /%	Al₂O₃ /%	Na₂O /%	SiO₂/Al₂O₃（摩尔比）	Al浓度 /mmol·g^-1	总酸量 /mmol·g^-1
ZSM-5-60	86.85	4.01	0.03	37	0.786	0.543
ZSM-5-100	93.68	1.50	0.20	106	0.295	0.463
ZSM-5-150	95.78	0.86	0.06	189	0.168	0.262
ZSM-5-200	95.47	0.64	0.07	254	0.126	0.272
ZSM-5-400	94.77	0.38	0.03	424	0.075	0.190

表2 不同硅铝比ZSM-5吡啶红外表征结果

样品	总酸量（200℃脱附） /μmol·g^-1			中强酸量（350℃脱附） /μmol·g^-1
样品	L酸	B 酸	B/L	L酸	B 酸	B/L
ZSM-5-60	28.7	492.6	17.2	25.7	366.3	14.3
ZSM-5-100	39.6	153.2	3.9	19.3	112.4	5.8
ZSM-5-150	15.7	91.7	5.8	14.2	70.6	5.0
ZSM-5-200	8.6	49.4	5.7	6.4	36.7	5.7
ZSM-5-400	17.6	29.0	1.6	12.4	19.5	1.6

图2 不同硅铝比ZSM-5的SEM图

图3 不同ZSM-5硅铝比（SiO2/Al2O3）对TOX转化率和PODE选择性的影响（催化剂2%，nDMM/nTOX=3∶1，600r/min，100℃，30min，0.60MPa）

图4 催化剂成型配方中SiO2质量分数对ZSM-5成型催化剂径向压碎强度的影响

图5 MC分子量对ZSM-5成型催化剂径向压碎强度的影响

图6 ZSM-5成型催化剂照片

图7 不同批次ZSM-5成型催化剂的径向压碎强度

图8 反应温度对选择性和转化率的影响

（nDMM∶nTOX=2.5∶1，LHSV=4.5h-1，P=1MPa）

图9 液体空速对选择性和转化率的影响

（nDMM∶nTOX=2.5∶1，T.=85℃，P=1MPa）

图10 三聚甲醛转化率、PODE和MF选择性随反应时间的变化

（nDMM∶nTOX=2.5∶1，T.=85℃，P=1MPa）

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